Diversity and Complexity through Reversible Multiple Orthogonal Interactions in Multicomponent Assemblies

Abstract

Solving the puzzle of how to piece together the building blocks of a multicomponent aggregate should become easier by an improved mastery of reversible orthogonal interactions. In this way the complexity and emergence of artificial multicomponent assemblies may approach those of natural systems.

A Light‐Harvesting Antenna Resulting from the Self‐Assembly of Five Luminescent Components: A Dendrimer, Two Clips, and Two Lanthanide Ions

“…The value of h Nd is much lower because of the presence of groups that have high energy vibrations in the dendrimer. On the other hand, the dendrimer is able to encapsulate lanthanide ions so efficiently that no change in Nd 3 + emission is observed upon using deuterated solvents, that is, CD 3 …”

“…The value of the resulting supramolecular system relies not only on the total number of self-assembled molecules, but also on the diversity of the components and on the functions that result from their mutual interactions. [3] Here, we report on the self-assembly of five luminescent components of three different types, which results in an efficient light-harvesting antenna system. The three different species involved are: dendrimer D (Scheme 1), composed of a polylysin scaffold to which 24 dansyl units are appended; [4] clip C (Scheme 1), which presents two anthracene sidewalls Abstract: We have investigated the self-assembly of three luminescent species in CH 3 CN/CH 2 Cl 2 , namely: 1) a polylysin dendrimer (D) composed of 21 aliphatic amide units and 24 green luminescent dansyl chromophores at the periphery, 2) a molecular clip (C) with two blue luminescent anthracene sidewalls and a benzene bridging unit that bears two sulfate groups in the para position, and 3) a near infrared (NIR)-emitting Nd 3 + ion.…”

Quadruple Switching of Pleated Foldamers of Tetrathiafulvalene–Bipyridinium Alternating Dynamic Covalent Polymers

“…The UV/Vis spectrum of P1 displayed two absorption bands at around 450 and 650 nm (Figure 3 a), which could be assigned to the BIPYC + monomer. [17] The spectrum also showed a band at around 985 nm. This band was not generated by monomeric M1 a with the same BIPYC + concentration (see the Supporting Information).…”

“…Recently, it was demonstrated that the homodimerization of conjugated radical cations is highly orthogonal. [16,17] Herein, we describe how the folding-unfolding process of two tetrathiafulvalene (TTF)-bipyridinium (BIPY 2+ ) alternating dynamic covalent polymers P1 and P2 can be modulated in four different ways by donor-acceptor interactions and radical-cation dimerization.Polymers P1 and P2 were conveniently prepared from dialdehyde M1 a or M1 b and the di(acylhydrazine) M2 in MeCN through the formation of acylhydrazones: a wellestablished dynamic covalent approach for the generation of dynamic polymers.[18] Polymers P1 and P2 were soluble in MeCN. Their average degree of polymerization was determined to be approximately 8 and 6, respectively, by 1 H NMR spectroscopy in [D 3 ]MeCN on the basis of the relative integrals of the signals for the aldehyde hydrogen atom and the a hydrogen atoms of the BIPY 2+ units (see the Supporting Information).…”

“…An EPR signal was observed for monomeric TTFC + [22] and was nearly identical for samples of P1, P2, and monomer M2 in MeCN (see the Supporting Information). The UV/Vis spectra of P1 and P2 did not show the absorption band of the dimer (TTFC + ) 2 , [17] even at the saturation concentration (about 1.0 mm ; see the Supporting Information). Moreover, for both polymers, the strength of the EPR signal of monomeric TTFC + was linearly related to the concentration.…”